Patent GB-1249350-A (GB)
Title: Improvements in and relating to heat-developable diazotype material
IPC: G03C1/54
Filed: 1968-10-25
Abstract: 1,249,350. Diazonium and quinone diazide compounds. KALLE A.G. 25 Oct., 1968 [28 Oct., 1967], No. 50688/68. Heading C2C. [Also in Division G2] 1 - (21 - Diazophenyl) - 3 - methyl pyrazolone (5) is prepared by diazotizing and reducing 2- nitroaniline to 2-nitro-phenylhydrazine. The phenylhydrazine is reacted with acetoacetic ester under reduced pressure to give the hydrazone. The corresponding 1-(4<SP>1</SP>-diazophenyl)-3- methyl pyrazolone (5) is prepared similarly using 4 - nitroaniline. Naphthoquinone (1,2)- diazide (2) - 5 - sulphonic acid (3<SP>1</SP> hydroxy)- naphthyl (2<SP>1</SP>)-ester is prepared by adding dropwise 2,3-dihydroxy-naphthalene and sodium methylate to naphthoquinone (1,2)-diazide (2)- 5-sulphochloride. Other esters or amide are prepared by using phloroglucinol; 3-aminophenol; 1-amino-6-naphthol; 2,7-dihydroxynaphthalene; 2-amino-7-sulpho-8-naphthol and 2,3,4 - trihydroxynaphthalene 6 - sulphonic acid. 4 - Morpholino - 3 - [3<SP>1</SP> (3<SP>11</SP> - hydroxyphenylamine) - 2<SP>1</SP> - hydroxy - n - propoxy]- benzene diazonium chloride is prepared by reacting 5 - nitro - 2 - morpholino - phenyl- 2<SP>1</SP>,3<SP>1</SP> - epoxy - 1 - propyl ether with m - aminophenol and then reducing- and diazotizing the nitro compound thus produced. 6 - Dimethylamino - 3 - diazo - benzoic acid- 7<SP>1</SP> - hydroxynaphthyl - (2<SP>1</SP>) -  amide is produced by reacting 6-chloro-3-nitrobenzoic acid with dimethylamine to give 6-dimethylamino-3-nitrobenzoic acid. The acid is treated with thionyl chloride and the acid chloride produced is reacted with 2-amino-7-naphthol. The nitro compound is reduced and diazotized. 2,7 Dihydroxynaphthalene may replace the 2- amino-7-naphthol so that the corresponding ester is produced. 3 - Hydroxy - 2 - naphthoic acid - [N - (4<SP>1</SP>- diazo)-phenyl]-piperazide is prepared by reacting N - (4 - nitrophenyl) - piperazine with 3- hydroxy-2-naphthoic acid chloride and then reducing and diazotizing the nitro compound produced. The corresponding 3-methylphenyl piperazide is prepared by using N-(4-nitro-3- methyl-phenyl)-piperazine. 4 - Pyrrolidino - 3 - [3<SP>1</SP> - hydroxy - naphthoyl- (2<SP>1</SP>) - amino] - benzene diazonium chloride is prepared by reacting 4-chloro-1,3-dinitrobenzene with pyrrolidine and reducing the product to give 5-nitro-2-pyrrolidino-aniline. This is reacted with 3-hydroxy-2-naphthoic acid chloride to give 5 - nitro - 2 - pyrrolidino - 3 - [3<SP>1</SP>- hydroxy - naphthoyl - (2<SP>1</SP>) - amino] - benzene which on reduction and diazotization gives the diazo compound. 5 - Diazo - 2 - pyrrolidino - phenyl - # - [N- ethyl - N - (3<SP>1</SP> - hydroxynaphthoyl - (2<SP>1</SP>) - amino)]- ethyl ether is prepared by reacting 6-chloro-3- nitrophenol with ethylene bromide and the product reacted with ethylamine to give 6 - chloro - 3 - nitro - phenyl - (# - ethylamino)- ethyl-ether. The ether is reacted with pyrrolidine and the product reacted with 3-hydroxy-2- naphthoic acid chloride to give 6-pyrrolidino- 3 - nitro - phenyl - # - [N - ethyl - N - 3<SP>1</SP> - hydroxynaphthoyl - (2<SP>1</SP>)- amino] - ethyl ether. This ether on reduction and diazotization gives the corresponding diazo compound. 4 - (N - Methyl- N - benzyl) - amino - 3 - [3<SP>1</SP> - hydroxynaphthoyl - (2<SP>1</SP>) - amino] - benzene diazonium chloride is prepared by reacting 4-chloro-1,3-dinotro-benzene with N-methyl-N-benzylamine and the product reduced to give 5-nitro-2-(N-methyl- N-benzyl)-amino-aniline. This is reacted with 3 - hydroxy - 2 - naphthoic acid chloride and the product reduced and diazotized to give the corresponding diazo compound.